Thermosetting polyurethane material for a golf ball cover

ABSTRACT

A prepolymer blend for a thermosetting polyurethane material that allows for control of the reaction time is disclosed herein. The prepolymer blend is preferably composed of a polyurethane prepolymer and dimethyl methylphosphonate. The thermosetting polyurethane is preferably utilized as a cover for a golf ball. The cover is preferably formed over a core and boundary layer.

CROSS REFERENCE TO RELATED APPLICATIONS

The Present Application is a continuation application of U.S. patentapplication Ser. No. 09/683,001, filed on Nov. 6, 2001 now U.S. Pat. No.6,607,686.

FEDERAL RESEARCH STATEMENT

[Not Applicable]

BACKGROUND OF INVENTION

1. Field of the Invention

The present invention relates to a thermosetting polyurethane material.More specifically, the present invention relates to a thermosettingpolyurethane material for a cover of a golf ball.

2. Description of the Related Art

Conventionally golf balls are made by molding a cover around a core. Thecore may be wound or solid. A wound core typically comprises elasticthread wound about a solid or liquid center. Unlike wound cores, solidcores do not include a wound elastic thread layer. Solid cores typicallymay comprise a single solid piece center or a solid center covered byone or more mantle or boundary layers of material.

The cover may be injection molded, compression molded, or cast over thecore. Injection molding typically requires a mold having at least onepair of mold cavities, e.g., a first mold cavity and a second moldcavity, which mate to form a spherical recess. In addition, a mold mayinclude more than one mold cavity pair.

In one exemplary injection molding process each mold cavity may alsoinclude retractable positioning pins to hold the core in the sphericalcenter of the mold cavity pair. Once the core is positioned in the firstmold cavity, the respective second mold cavity is mated to the first toclose the mold. A cover material is then injected into the closed mold.The positioning pins are retracted while the cover material is flowableto allow the material to fill in any holes caused by the pins. When thematerial is at least partially cured, the covered core is removed fromthe mold.

As with injection molding, compression molds typically include multiplepairs of mold cavities, each pair comprising first and second moldcavities that mate to form a spherical recess. In an exemplarycompression molding process, a cover material is pre-formed intohalf-shells, which are placed into a respective pair of compression moldcavities. The core is placed between the cover material half-shells andthe mold is closed. The core and cover combination is then exposed toheat and pressure, which cause the cover half-shells to combine and forma full cover.

As with the above-referenced processes, a casting process also utilizespairs of mold cavities. In a casting process, a cover material isintroduced into a first mold cavity of each pair. Then, a core is heldin position (e.g. by an overhanging vacuum or suction apparatus) tocontact the cover material that will be the spherical center of the moldcavity pair. Once the cover material is at least partially cured (e.g.,a point where the core will not substantially move), the core isreleased, the cover material is introduced into a second mold cavity ofeach pair, and the mold is closed. The closed mold is then subjected toheat and pressure to cure the cover material thereby forming a cover onthe core. With injection molding, compression molding, and casting, themolding cavities typically include a negative dimple pattern to impart adimple pattern on the cover during the molding process.

Materials previously used as golf ball covers include balata (natural orsynthetic), gutta-percha, ionomeric resins (e.g., DuPont's SURLYN®), andpolyurethanes. Balata is the benchmark cover material with respect tosound (i.e. the sound made when the ball is hit by a golf club) and feel(i.e. the sensation imparted to the golfer when hitting the ball).Natural balata is derived from the Bully Gum tree, while syntheticbalata is derived from a petroleum compound. Balata is expensivecompared to other cover materials, and golf balls covered with balatatend to have poor durability (i.e. poor cut and shear resistance). Guttapercha is derived from the Malaysian sapodilla tree. A golf ball coveredwith gutta percha is considered to have a harsh sound and feel ascompared to balata covered golf balls.

Ionomeric resins, as compared to balata, are typically less expensiveand tend to have good durability. However, golf balls having ionomericresin covers typically have inferior sound and feel, especially ascompared to balata covers.

A golf ball with a polyurethane cover generally has greater durabilitythan a golf ball with a balata cover. The polyurethane covered golf ballgenerally has a better sound and feel than a golf ball with an ionomericresin cover. Polyurethanes may be thermoset or thermoplastic.Polyurethanes are formed by reacting a prepolymer with a polyfunctionalcuring agent, such as a polyamine or a polyol. The polyurethaneprepolymer is the reaction product of, for example, a diisocyanate and apolyol such as a polyether or a polyester. Several patents describe theuse of polyurethanes in golf balls. However, golf balls withpolyurethane covers usually do not have the distance of other golf ballssuch as those with covers composed of SURLYN® materials.

Gallagher, U.S. Pat. No. 3,034,791 discloses a polyurethane golf ballcover prepared from the reaction product of poly(tetramethylene ether)glycol and toluene-2,4-diisocyanates (TDI), either pure TDI or anisomeric mixture.

Isaac, U.S. Pat. No. 3,989,568 (the '568 patent) discloses apolyurethane golf ball cover prepared from prepolymers and curing agentsthat have different rates of reaction so a partial cure can be made. The'568 patent explains that “the minimum number of reactants is three”.Specifically, in '568 patent, two or more polyurethane prepolymers arereacted with at least one curing agent, or at least one polyurethaneprepolymer is reacted with two or more curing agents as long as thecuring agents have different rates of reaction. The '568 patent alsoexplains that “[o]ne of the great advantages of polyurethane covers madein accordance with the instant invention is that they may be made verythin . . . ”, and “[t] here is no limitation on how thick the cover ofthe present invention may be but it is generally preferred . . . thatthe cover is no more than about 0.6 inches in thickness”. The examplesin the '568 patent only disclose golf balls having covers that are about0.025 inches thick.

Similar to Isaac, PCT International Publication Number WO 99/43394 toDunlop Maxfli Sports Corporation, discloses using two curing agents tocontrol the reaction time for polyurethane formation. The two curingagents are a dimethylthio 2,4-toluenediamine and diethyl2,4-toluenediamine, which are blended to control the reaction rate of atoluene diisocyanate based polyurethane prepolymer or a4,4′-diphenylmethane diisocyanate based polyurethane prepolymer.

Dusbiber, U.S. Pat. No. 4,123,061 (the '061 patent) discloses apolyurethane golf ball cover prepared from the reaction product of apolyether, a diisocyanate and a curing agent. The '061 patent disclosesthat the polyether may be polyalkylene ether glycol orpolytetramethylene ether glycol. The '061 patent also discloses that thediisocyanate may be TDI, 4,4′-diphenylmethane diisocyanate (“MDI”), and3,3′-dimethyl-4,4′-biphenylene diisocyanate (“TODI”). Additionally, the'061 patent discloses that the curing agent may be either a polyol(either tri- or tetra-functional and not di-functional) such astriisopropanol amine (“TIPA”) or trimethoylol propane (“TMP”), or anamine-type having at least two reactive amine groups such as: 3,3′dichlorobenzidene; 3,3′ dichloro 4,4′ diamino diphenyl methane (“MOCA”);N,N,N′,N′ tetrakis (2-hydroxy propyl) ethylene diamine; or Uniroyal'sCuralon L which is an aromatic diamine mixture.

Hewitt, et al., U.S. Pat. No. 4,248,432 (the '432 patent) discloses athermoplastic polyesterurethane golf ball cover formed from a reactionproduct of a polyester glycol (molecular weight of 800-1500) (aliphaticdiol and an aliphatic dicarboxylic acid) with a para-phenylenediisocyanate (“PPDI”) or cyclohexane diisocyanate in the substantialabsence of curing or crosslinking agents. The '432 patent teachesagainst the use of chain extenders in making polyurethanes. The '432patent states, “when small amounts of butanediol-1,4 are mixed with apolyester . . . the addition results in polyurethanes that do not havethe desired balance of properties to provide good golf ball covers.Similarly, the use of curing or crosslinking agents is not desired . . ..”

Holloway, U.S. Pat. No. 4,349,657 (the '657 patent) discloses a methodfor preparing polyester urethanes with PPDI by reacting a polyester(e.g. prepared from aliphatic glycols having 2-8 carbons reacted withaliphatic dicarboxylic acids having 4-10 carbons) with a molar excess ofPPDI to obtain an isocyanate-terminated polyester urethane (in liquidform and stable at reaction temperatures), and then reacting thepolyester urethane with additional polyester. The '657 patent claimsthat the benefit of this new process is the fact that a continuouscommercial process is possible without stability problems. The '657patent further describes a suitable use for the resultant material to begolf ball covers.

Wu, U.S. Pat. No. 5,334,673 (the '673 patent) discloses a polyurethaneprepolymer cured with a slow-reacting curing agent selected fromslow-reacting polyamine curing agents and difunctional glycols (i.e.,3,5-dimethylthio-2,4-toluenediamine,3,5-dimethylthio-2,6-toluenediamine, N,N′-dialkyldiamino diphenylmethane, trimethylenegly-col-di-p-aminobenzoate,polytetramethyleneoxidedi-p-aminobenzoate, 1,4-butanediol,2,3-butanediol, 2,3-dimethyl-2,3-butanediol, ethylene glycol, andmixtures of the same). The polyurethane prepolymer in the '673 patent isdisclosed as made from a polyol (e.g., polyether, polyester, orpolylactone) and a diisocyanate such as MDI or TODI. The polyetherpolyols disclosed in the '673 patent are polytetramethylene etherglycol, poly(oxypropylene) glycol, and polybutadiene glycol. Thepolyester polyols disclosed in the '673 patent are polyethylene adipateglycol, polyethylene propylene adipate glycol, and polybutylene adipateglycol. The polylactone polyols disclosed in the '673 patent arediethylene glycol initiated caprolactone, 1,4-butanediol initiatedcaprolactone, trimethylol propane initiated caprolactone, and neopentylglycol initiated caprolactone.

Cavallaro, et al., U.S. Pat. No. 5,688,191 discloses a golf ball havingcore, mantle layer and cover, wherein the mantle layer is either avulcanized thermoplastic elastomer, functionalized styrene-butadieneelastomer, thermoplastic polyurethane, metallocene polymer or blends ofthe same and thermoset materials.

Wu, et al., U.S. Pat. No. 5,692,974 discloses golf balls having coversand cores that incorporate urethane ionomers (i.e. using an alkylatingagent to introduce ionic interactions in the polyurethane and therebyproduce cationic type ionomers).

Sullivan, et al., U.S. Pat. No. 5,803,831 (the '831 patent) discloses agolf ball having a multi-layer cover wherein the inner cover layer has ahardness of at least 65 Shore D and the outer cover layer has a hardnessof 55 Shore D or less, and more preferably 48 Shore D or less. The '831patent explains that this dual layer construction provides a golf ballhaving soft feel and high spin on short shots, and good distance andaverage spin on long shots. The '831 patent provides that the innercover layer can be made from high or low acid ionomers such as SURLYN®,ESCOR® or IOTEK®, or blends of the same, nonionomeric thermoplasticmaterial such as metallocene catalyzed polyolefins or polyamides,polyamide/ionomer blends, polyphenylene ether/ionomer blends, etc.,(having a Shore D hardness of at least 60 and a flex modulus of morethan 30000 psi), thermoplastic or thermosetting polyurethanes, polyesterelastomers (e.g. HYTREL®), or polyether block amides (e.g. PEBAX®), orblends of these materials. The '831 patent also provides that the outercover layer can be made from soft low modulus (i.e. 1000-10000 psi)material such as low-acid ionomers, ionomeric blends, non-ionomericthermoplastic or thermosetting materials such as polyolefins,polyurethane (e.g. thermoplastic polyurethanes like TEXIN®, PELETHANE®,and thermoset polyurethanes like those disclosed in Wu, U.S. Pat. No.5,334,673), polyester elastomer (e.g. HYTREL®), or polyether block amide(e.g. PEBAX®), or a blend of these materials.

Hebert, et al., U.S. Pat. No. 5,885,172 (the '172 patent) discloses amultilayer golf ball giving “a progressive performance” (i.e. differentperformance characteristics when struck with different clubs atdifferent head speeds and loft angles) and having an outer cover layerformed of a thermoset material with a thickness of less than 0.05 inchesand an inner cover layer formed of a high flexural modulus material. The'172 patent provides that the outer cover is made from polyurethaneionomers as described in Wu, et al., U.S. Pat. No. 5,692,974, orthermoset polyurethanes such as TDI or methylenebis-(4-cyclohexylisocyanate) (“HMDI”), or a polyol cured with a polyamine (e.g.methylenedianiline (MDA)), or with a tri-functional glycol (e.g.,N,N,N′,N′-tetrakis(2-hydroxpropyl)ethylenediamine). The '172 alsoprovides that the inner cover has a Shore D hardness of 65-80, aflexural modulus of at least about 65,000 psi, and a thickness of about0.020-0.045 inches. Exemplary materials for the inner cover areionomers, polyurethanes, polyetheresters (e.g. HYTREL®), polyetheramides(e.g., PEBAX®), polyesters, dynamically vulcanized elastomers,functionalized styrene-butadiene elastomer, metallocene polymer, blendsof these materials, nylon or acrylonitrile-butadiene-styrene copolymer.

Wu, U.S. Pat. No. 5,484,870 (the '870 patent) discloses golf ballshaving covers composed of a polyurea composition. The polyureacomposition disclosed in the '870 patent is a reaction product of anorganic isocyanate having at least two functional groups and an organicamine having at least two functional groups. One of the organicisocyanates disclosed by the '870 patent is PPDI.

Although the prior art has disclosed golf ball covers composed of manydifferent polyurethane materials, none of these golf balls have provencompletely satisfactory. Dissatisfaction, for example, remains withprocessing and manufacturing the balls, especially with controlling thereaction time of the curative and prepolymer. If the gel time forformation of a polyurethane material is too fast, the time to place acore in a hemispherical cavity with the gelling pre-polyurethanematerial and to mate the hemispherical cavity with a correspondinghemispherical cavity is greatly reduced thereby leading to processingproblems like air pockets, and centering of the core.

SUMMARY OF INVENTION

The present invention provides a novel solution to the problem ofcontrolling the reaction time of formation of a polyurethane material.The solution is the use of dimethyl methylphosphonate as a component ofthe prepolymer blend to lower the viscosity of a polyurethaneprepolymer, thereby allowing the use of a fast curing agent, likediethyl 2,4-toluenediamine. The lowered viscosity allows for thereaction temperature to be lowered thereby decreasing the gel time forthe polyurethane formation. There is a desire to use curing agents suchas diethyl 2,4-toluenediamine because such curing agents providepolyurethane materials with less yellowing and greater durability.

One aspect of the present invention is a golf ball including a core anda cover. The cover is composed of a thermosetting polyurethane materialformed from reactants composed of prepolymer blend including apolyurethane prepolymer and dimethyl methylphosphonate, and a curativeincluding at least one primary curing agent. The cover has anaerodynamic surface geometry thereon.

Another aspect of the present invention is a golf ball including a core,a boundary layer and a cover. The core is a polybutadiene mixture andhas a diameter ranging from 1.35 inches to 1.64 inches. The core alsohas a PGA compression ranging from 50 to 90. The boundary layer isformed over the core and is composed of a blend of ionomer materials.The boundary layer has a thickness ranging from 0.020 inch to 0.075 inchand a Shore D hardness ranging from 50 to 75 as measured according toASTM-D2240. The cover is formed over the boundary layer. The cover iscomposed of a thermosetting polyurethane material formed from reactantsincluding a prepolymer blend composed of a polypropylene glycolterminated toluene diisocyanate prepolymer and 1 to 10 parts dimethylmethylphosphonate, and a curative blend including 20 to 40 parts4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline and 80 to 60 partsdiethyl 2,4-toluenediamine. The cover has a Shore D hardness rangingfrom 30 to 60 as measured according to ASTM-D2240. The cover also has athickness ranging from 0.015 inch to 0.040 inch and an aerodynamicsurface geometry thereon.

Having briefly described the present invention, the above and furtherobjects, features and advantages thereof will be recognized by thoseskilled in the pertinent art from the following detailed description ofthe invention when taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates a perspective view of a golf ball of the presentinvention including a cut-away portion showing a core, a boundary layer,and a cover.

FIG. 2 illustrates a perspective view of a golf ball of the presentinvention including a cut-away portion core and a cover.

DETAILED DESCRIPTION

The polyurethane material of the present invention is formed fromreactants comprising a prepolymer blend including a polyurethaneprepolymer and dimethyl methylphosphonate, and a curative blendcomprising a primary curing agent. The dimethyl methylphosphonate ispreferably present in an amount of 1 to 10 parts per one hundred partsof the polyurethane prepolymer, and most preferably 5 parts per onehundred parts of the polyurethane prepolymer. The primary curing agentis preferably diethyl 2,4-toluenediamine. The polyurethane prepolymer ispreferably selected from toluene diisocyanate-based polyurethaneprepolymers, para-phenylene diisocyanate-based polyurethane prepolymers,and 4,4′-diphenylmethane diisocyanate-based polyurethane prepolymers.The polyurethane prepolymer is preferably utilized alone or in a blendof two or three polyurethane prepolymers. A preferred use of thecurative blend is in the formation of thermosetting polyurethane for thecover of a golf ball.

As illustrated in FIG. 1, a golf ball is generally indicated as 10. Thegolf ball 10 includes a core 12, a boundary layer 14 and a cover 16.Alternatively, as shown in FIG. 2, the golf ball 10 may only include acore 12 and a cover 16. The cover 16 is composed of a thermosettingpolyurethane material of the present invention. In a preferredembodiment, the cover 16 is formed over a boundary layer 14 and core 12,as shown in FIG. 1. Alternatively, the cover 16 is formed over the core12, as shown in FIG. 2. Those skilled in the art will recognize that thecore may be solid, hollow, multi-piece or liquid-filled, and theboundary layer may be partitioned into additional layers, withoutdeparting from the scope and spirit of the present invention.

The prepolymer blend for a thermosetting polyurethane material of thepresent invention utilizes dimethyl methylphosphonate to lower theviscosity of the polyurethane prepolymer to control the reaction to formthe polyurethane. A preferred dimethyl methylphosphonate is FYROL DMMPavailable from Akzo Nobel Chemicals of Chicago, Ill. The dimethylmethylphosphonate is blended with at least one polyurethane prepolymerto form the prepolymer blend, however multiple polyurethane prepolymersmay be utilized in the prepolymer blend.

As mentioned previously, the preferred primary curing agent is diethyl2,4-toluenediamine, which is available from Albemarle Corporation ofBaton Rouge, La. under the tradename ETHACURE® 100.4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline, which is availablefrom Air Products and Chemicals Inc., of Allentown, Pa., under thetradename LONZACURE™, is mixed with the diethyl 2,4-toluenediamine in analternative embodiment of the curative blend.

The thermosetting polyurethane material is preferably formed from atoluene diisocyanate prepolymer mixed with dimethyl methylphosphonate.The toluene diisocyanate prepolymer is preferably a polypropylene glycolterminated toluene diisocyanate prepolymer or a polytetramethylene etherglycol terminated toluene diisocyanate prepolymer. A preferredpolypropylene glycol terminated toluene diisocyanate prepolymer isavailable from Uniroyal Chemical Company of Middlebury, Conn., under thetradename ADIPRENE® LFG960. A preferred polytetramethylene ether glycolterminated toluene diisocyanate prepolymer is available from UniroyalChemical Company of Middlebury, Conn., under the tradename ADIPRENE®LF930. Another toluene diisocyanate prepolymer is a toluene diisocyanateterminated polyether prepolymer available from Uniroyal Chemical Companyof Middlebury, Conn., under the tradename ADIPRENE® LF950. The use ofmultiple polyurethane prepolymers is set forth in U.S. Pat. No.6,190,268, entitled Golf Ball With A Polyurethane Cover, filed on Jul.27, 1999, assigned to Callaway Golf Company, and which is herebyincorporated by reference in its entirety.

The dimethyl methylphosphonate is also utilized with a para-phenylenediisocyanate-based polyurethane prepolymer. An example is apara-phenylene diisocyanate terminated polyester prepolymer, which isavailable from Uniroyal Chemical under the tradename ADIPRENE® LFPX2950. Another is a para-phenylene diisocyanate terminated polyetherprepolymer, which is available from Uniroyal Chemical under thetradename ADIPRENE® LFPX 950.

The dimethyl methylphosphonate is preferably utilized with a singlepolyurethane prepolymer, a di-blend of polyurethane prepolymers, or atri-blend of polyurethane prepolymers. However, those skilled in thepertinent art will recognize that greater multiples of polyurethaneprepolymers may be utilized with the present invention without departingfrom the scope and spirit of the claims.

In a preferred embodiment, the curative blend is composed of 100 partsdiethyl 2,4-toluenediamine. In an alternative embodiment, the curativeblend is composed of 20 to 40 parts4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline, and 80 to 60 partsdiethyl 2,4-toluenediamine. A most preferred curative blend of thisalternative embodiment is composed of 30 parts4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline and 70 parts diethyl2,4-toluenediamine.

The ratio of the polyurethane prepolymer to curative is determined bythe nitrogen-carbon-oxygen group (“NCO”) content of the polyurethaneprepolymer. For example, the NCO content of the polypropylene glycolterminated toluene diisocyanate prepolymer is preferably in the range of3.0% to 6.0%, more preferably in the range of 4.0% to 5.75%, and mostpreferably 5.70%. The NCO content of the polytetramethylene ether glycolterminated toluene diisocyanate prepolymer is preferably in the range of3.75% to 7.0%, more preferably in the range of 4.0% to 5.75%, and mostpreferably 5.70%. The weight ratio of the polyurethane prepolymer to thecurative is preferably in the range of about 10:1 to about 30:1.

Prior to curing, the polyurethane prepolymer and curative blend arepreferably stored separately. In general, the polyurethane material isformed by first heating and mixing the curative blend. Then, thepolyurethane prepolymer and the curative blend are mixed in a chamber.The mixture from the chamber is dispensed into a hemispherical cavityprior to insertion of a golf ball precursor product. Thepre-polyurethane material is cured by applying heat and pressure for apredetermined period of time. A more specific process is set forthbelow.

The prepolymer blend is preferably degassed and warmed in a firstholding container. The processing temperature for the prepolymer blendis preferably in the range of about 70-130° F., and most preferably inthe range of about 80-120° F. The prepolymer blend is preferablyflowable from the first holding container to a mixing chamber in a rangeof about 200-1100 grams of material per minute, or as needed forprocessing. In addition, the prepolymer material may be agitated in thefirst holding container, in the range of 0-250 rpm, to maintain a moreeven distribution of material and to eliminate crystallization.

The curative blend is degassed and warmed in a second holding container.The processing temperature for the curative blend is preferably in therange of about 50-230° F., and most preferably in the range of about80-200° F. The curative is preferably flowable from the second holdingcontainer to the mixing chamber in the range of about 15-75 grams ofmaterial per minute, or as needed. Additives may be added to thecurative blend as desired.

The polyurethane prepolymer and curative blend is preferably added tothe common mixing chamber at a temperature in the range of about160-220° F. A colorant material, such as, for example, titanium dioxide,barium sulfate, and/or zinc oxide in a glycol or castor oil carrier,and/or other additive material(s) as are well known in the art, may beadded to the common mixing chamber. The amount of colorant materialadded is preferably in the range of about 0-10% by weight of thecombined polyurethane prepolymer and curative materials, and morepreferably in the range of about 2-8%. Other additives, such as, forexample, polymer fillers, metallic fillers, and/or organic and inorganicfillers (e.g. polymers, balata, ionomers, etc.) may be added as well toincrease the specific gravity of the polyurethane material. The entiremixture is preferably agitated in the mixing chamber in the range ofabout 1 to 250 rpm prior to molding. A more detailed explanation of oneaspect of the process is set forth in U.S. Pat. No. 6,200,512, entitledGolf Balls And Methods Of Manufacturing The Same, filed on Apr. 20,1999, assigned to Callaway Golf Company, and which is herebyincorporated by reference in its entirety. A more detailed explanationof the casting system is set forth in co-pending U.S. patent applicationSer. No. 09/496,126, entitled System And Method For Forming A ThermosetGolf Ball Cover, filed on Feb. 1, 2000, assigned to Callaway GolfCompany, and which is hereby incorporated by reference in its entirety.

The cover 16 is formed over a golf ball precursor product, which iseither a core, a core with at least one boundary layer, or a core withwindings. The core 12 of the golf ball 10 is the “engine” for the golfball 10 such that the inherent properties of the core 12 will stronglydetermine the initial velocity and distance of the golf ball 10. Ahigher initial velocity will usually result in a greater overalldistance for a golf ball. In this regard, the Rules of Golf, approved bythe United States Golf Association (“USGA”) and The Royal and AncientGolf Club of Saint Andrews, limits the initial velocity of a golf ballto 250 feet (76.2 m) per second (a two percent maximum tolerance allowsfor an initial velocity of 255 per second) and the overall distance to280 yards (256 m) plus a six percent tolerance for a total distance of296.8 yards (the six percent tolerance may be lowered to four percent).A complete description of the Rules of Golf is available on the USGA webpage at www.usga.org. Thus, the initial velocity and overall distance ofa golf ball must not exceed these limits in order to conform to theRules of Golf. Therefore, the core 12 for a USGA approved golf ball isconstructed to enable the golf ball 10 to meet, yet not exceed, theselimits.

The coefficient of restitution (“COR”) is a measure of the resilience ofa golf ball. The COR is a measure of the ratio of the relative velocityof the golf ball after direct impact with a hard surface to the relativevelocity before impact with the hard surface. The COR may vary from 0 to1, with 1 equivalent to a completely elastic collision and 0 equivalentto a completely inelastic collision. A golf ball having a COR valuecloser to 1 will generally correspond to a golf ball having a higherinitial velocity and a greater overall distance. If the golf ball has ahigh COR (more elastic), then the initial velocity of the golf ball willbe greater than if the golf ball has a low COR. In general, a highercompression core will result in a higher COR value.

The core 12 of the golf ball 10 is generally composed of a blend of abase rubber, a cross-linking agent, a free radical initiator, and one ormore fillers or processing aids. A preferred base rubber is apolybutadiene having a cis-1,4 content above 90%, and more preferably98% or above.

The use of cross-linking agents in a golf ball core is well known, andmetal acrylate salts are examples of such cross-linking agents. Forexample, metal salt diacrylates, dimethacrylates, or mono(meth)acrylatesare preferred for use in the golf ball cores of the present invention,and zinc diacrylate is a particularly preferred cross-linking agent. Acommercially available suitable zinc diacrylate is SR-416 available fromSartomer Co., Inc., Exton, Pa. Other metal salt di- ormono-(meth)acrylates suitable for use in the present invention includethose in which the metal is calcium or magnesium. In the manufacturingprocess it may be beneficial to pre-mix some cross-linking agent(s),such as, e.g., zinc diacrylate, with the polybutadiene in a master batchprior to blending with other core components.

Free radical initiators are used to promote cross-linking of the baserubber and the cross-linking agent. Suitable free radical initiators foruse in the golf ball core 12 of the present invention include peroxidessuch as dicumyl peroxide, bis-(t-butyl peroxy) diisopropyl benzene,t-butyl perbenzoate, di-t-butyl peroxide,2,5-dimethyl-2,5-di-5-butylperoxy-hexane, 1,1-di (t-butylperoxy)3,3,5-trimethyl cyclohexane, and the like, all of which are readilycommercially available.

Zinc oxide is also preferably included in the core formulation. Zincoxide may primarily be used as a weight adjusting filler, and is alsobelieved to participate in the cross-linking of the other components ofthe core (e.g. as a coagent). Additional processing aids such asdispersants and activators may optionally be included. In particular,zinc stearate may be added as a processing aid (e.g. as an activator).Any of a number of specific gravity adjusting fillers may be included toobtain a preferred total weight of the core 12. Examples of such fillersinclude tungsten and barium sulfate. All such processing aids andfillers are readily commercially available. The present inventors havefound a particularly useful tungsten filler is WP102 Tungsten (having a3 micron particle size) available from Atlantic Equipment Engineers (adivision of Micron Metals, Inc.), Bergenfield, N.J.

Table One below provides the ranges of materials included in thepreferred core formulations of the present invention.

TABLE ONE Component Preferred Range Most Preferred Range Polybutadiene   100 parts    100 parts Zinc diacrylate   20-35 phr   25-30 phr Zincoxide    0-50 phr    5-15 phr Zinc stearate    0-15 phr    1-10 phrPeroxide 0.2-2.5 phr 0.5-1.5 phr Filler As desired As desired (e.g.tungsten) (e.g. 2-10 phr) (e.g. 2-10 phr)

In the present invention, the core components are mixed and compressionmolded in a conventional manner known to those skilled in the art. In apreferred form, the finished core 12 has a diameter of about 1.35 toabout 1.64 inches for a golf ball 10 having an outer diameter of 1.68inches. The core weight is preferably maintained in the range of about32 to about 40 g. The core PGA compression is preferably maintained inthe range of about 50 to 90 and most preferably about 55 to 80.

As used herein, the term “PGA compression” is defined as follows:PGA compression value=180−Riehle compression value

The Riehle compression value is the amount of deformation of a golf ballin inches under a static load of 200 pounds, multiplied by 1000.Accordingly, for a deformation of 0.095 inches under a load of 200pounds, the Riehle compression value is 95 and the PGA compression valueis 85.

As is described above, the present invention preferably includes atleast one boundary layer 14 that preferably is composed of athermoplastic (e.g. thermoplastic or thermoplastic elastomer) or a blendof thermoplastics (e.g. metal containing, non-metal containing or both).However, the golf ball 10 may have several boundary layers 14 disposedbetween the core 12 and the cover 16. Most preferably the boundary layer14 is composed of at least one thermoplastic that contains organic chainmolecules and metal ions. The metal ion may be, for example, sodium,zinc, magnesium, lithium, potassium, cesium, or any polar metal ion thatserves as a reversible cross-linking site and results in high levels ofresilience and impact resistance. Suitable commercially availablethermoplastics are ionomers based on ethylene copolymers and containingcarboxylic acid groups with metal ions such as described above. The acidlevels in such suitable ionomers may be neutralized to controlresiliency, impact resistance and other like properties. In addition,other fillers with ionomer carriers may be used to modify (e.g.preferably increase) the specific gravity of the thermoplastic blend tocontrol the moment of inertia and other like properties. Exemplarycommercially available thermoplastic materials suitable for use in aboundary layer 14 of a golf ball 10 of the present invention include,for example the following materials and/or blends of the followingmaterials: HYTREL® and/or HYLENE® products from DuPont, Wilmington,Del., PEBAX® products from Elf Atochem, Philadelphia, Pa., SURLYN®products from DuPont, and/or ESCOR® or IOTEK® products from ExxonChemical, Houston, Tex.

The Shore D hardness of the boundary layer 14 ranges from 50 to 75, asmeasured according to ASTM D2290. It is preferred that the boundarylayer 14, have a hardness of between about 55-70 Shore D. In a preferredembodiment, the boundary layer 14 has a Shore D hardness in the range of58-65. One reason for preferring a boundary layer 14 with a Shore Dhardness of 75 or lower is to improve the feel of the resultant golfball. It is also preferred that the boundary layer 14 is composed of ablend of SURLYN® ionomer resins.

SURLYN®8150, 9150, and 6320 are, respectively, an ionomer resin composedof a sodium neutralized ethylene/methacrylic acid, an ionomer resincomposed of a zinc neutralized ethylene/methacrylic acid, and an ionomerresin composed of a terpolymer of ethylene, methacrylic acid and n-butylacrylate partially neutralized with magnesium, all of which areavailable from DuPont, Polymer Products, Wilmington, Del.

Exemplary golf balls of the present invention were constructed andcompared to the unpainted CALLAWAY GOLF RULE 35 SOFTFEEL golf ball.Table Two and Table Three set forth the physical properties of theexemplary group of golf balls #1, #2 and #3. A dozen golf balls wereconstructed for each group #1, #2 and #3. Each of the boundary layers 14of the exemplary golf balls #1, #2 and #3 were composed of an ionomerblend of forty-five weight percent SURLYN 8150, forty-five weightpercent SURLYN 9150 and ten weight percent SURLYN 6350. The averagethickness of each of the boundary layers 14 of the exemplary golf balls#1, #2 and #3 was 0.0525 inch. The Shore D hardness of the boundarylayer 14 of the exemplary golf balls #1, #2 and #3 was 62 points. TheShore D hardness provided in Table Three below was determined accordingto ASTM D2240.

Each of the covers 16 of the exemplary group of golf balls #1 werecomposed of a prepolymer blend of 50 parts per weight ofpolytetramethylene ether glycol terminated toluene diisocyanateprepolymer (ADRIPRENE LF930), 50 parts per weight of polyetherterminated toluene diisocyanate prepolymer (ADRIPRENE LF950) anddimethyl methylphosphonate in an amount of 5 parts per hundred parts ofthe polyurethane prepolymers, and cured with a diethyl2,4-toluenediamine (E100). Each of the covers 16 of the exemplary groupof golf balls #2 were composed of a prepolymer blend of 100 parts perweight of polytetramethylene ether glycol terminated toluenediisocyanate prepolymer (ADRIPRENE LF930) and dimethyl methylphosphonatein an amount of 5 parts per hundred parts of the polyurethaneprepolymer, and cured with a diethyl 2,4-toluenediamine (E100). Each ofthe covers 16 of the exemplary group of golf balls #3 were composed of aprepolymer blend of 100 parts per weight of polypropylene glycolterminated toluene diisocyanate prepolymer (ADRIPRENE LFG960) anddimethyl methylphosphonate in an amount of 5 parts per hundred parts ofthe polyurethane prepolymers, and cured 30 parts4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline (LONZACURE) and 70parts diethyl 2,4-toluenediamine (E100). Each of the covers 16 of theexemplary group of golf balls #4, #5, #6 and #7 were composed of aprepolymer blend of 100 parts per weight of polytetramethylene etherglycol terminated toluene diisocyanate prepolymer (ADRIPRENE LF930) anddimethyl methylphosphonate in an amount of 2.5 parts per hundred partsof the polyurethane prepolymer, and cured with a diethyl2,4-toluenediamine (E100). The average thickness of each of the covers16 of the exemplary golf balls #1, #2 and #3 was 0.030 inch. The Shore Dhardness of the covers 16 of the exemplary golf balls #1, #2 and #3 was51 points. The COR at 143 feet per second of each of the exemplary golfballs #1, #2 and #3 was 79.42 points.

TABLE TWO Bound. Layer Cover Bound. Layer Cover Ball Shore D Shore DThickness Thickness COR Ball (points) (points) (inch) (inch) (points) 162 — 0.0525 0.03 78.80 2 62 50 0.0525 0.03 79.97 3 62 — 0.0525 0.0379.40 4 62 51 0.0525 0.03 — 5 62 51 0.0525 0.03 — 6 62 51 0.0525 0.03 —7 62 51 0.0525 0.03 —

The average weight of each of the exemplary golf balls #1, #2 and #3 was45.24 grams, 45.06 grams and 45.38 grams respectively. The average PGAcompression of each of the exemplary golf balls #1, #2 and #3 was 99points, 99 points and 101 points respectively. The average PGAcompression of each of the exemplary golf balls #4-190 7 was 100 points.The average diameter of each of the exemplary golf balls #1-190 7 wasapproximately 1.680 inches. The core diameter of each of the cores 12 ofeach of the exemplary golf balls #1-#7 was 1.515 inches. The PGAcompression of each of the cores 12 of each of the exemplary golf balls#1-#7 was 70 points.

TABLE THREE Ball Ball Average Core Core Weight Compression DiameterDiameter Compression Ball (grams) (points) (inches) (inches) (points) 145.24 99 1.680 1.515 70 2 45.06 99 1.679 1.515 70 3 45.38 101 1.6811.515 70 4 45.32 100 1.683 1.515 70 5 45.32 100 1.683 1.515 70 6 45.32100 1.683 1.515 70 7 45.32 100 1.683 1.515 70

Tables Four and Five compare the CALLAWAY GOLF RULE 35 SOFTFEEL golfball to the exemplary golf balls #4, #5, #6 and #7 of the presentinvention. All of the golf balls were unpainted. Exemplary golf balls #4and #6, and the RULE 35 SOFTFEEL #1 and #3 were post-cured in aconvention oven while exemplary golf balls #5 and #7, and the RULE 35SOFTFEEL #2 and #4 were post-cured in a Lanley oven. The golf balls weremeasured to determine the yellowing of the thermosetting polyurethanecovers after exposure to sunlight. The color of the cover of each of thegolf balls is determined using a HUNTER COLORIMETER model ULTRA SCAN XEand measuring the color on a L.a. b. scale. On the “L” scale, ameasurement of 100 corresponds to complete white while a measurement of0 corresponds to complete black. On the “a” scale, a negative numbercorresponds to a green color while a positive number corresponds to ared color. On the “b” scale, a negative number corresponds to a bluecolor while a positive number corresponds to a yellow color. Thus, themore positive the b measurement, the more yellow the cover. The golfballs were measured before exposure to sunlight, after four hours ofexposure to sunlight and after twenty-four hours of exposure tosunlight/night.

TABLE FOUR After 4 Hour Before Exposure Exposure Difference Ball L a* b*L a* b* L a* b* Rule 96.67 −1.44 4.6 79.38 6.66 36.35 −17.29 8.1 31.7535 Soft #1 Rule 95.31 −1.94 11.92 78.27 7.49 35.67 −17.04 9.43 23.75 35Soft #2 Ex. 4 95.37 −1.52 1.76 93.75 −2.04 8.37 −1.62 −0.52 6.61 Ex. 595.75 −2.16 4.61 94.66 −2.0 8.04 −1.09 0.16 3.43

TABLE FIVE After 24 Hour Before Exposure Exposure Difference Ball L a*b* L A* b* L a* b* Rule 95.42 −1.44 3.86 73.62 11.12 42.68 −21.8 12.5638.82 35 Soft #3 Rule 94.24 −1.82 11.16 72.08 11.83 41.37 −22.16 13.6530.21 35 Soft #4 Ex. 6 97.1 −1.53 2.66 94.59 −1.77 11.78 −2.51 −0.249.12 Ex. 7 94.62 −2.39 4.85 91.67 −1.71 16.14 −2.95 0.68 11.29

As is shown in Tables Four and Five, the exemplary golf balls #4 and #5of the present invention have a lower yellow measurement (“b” scale)before exposure, and a lower increase in yellowing after four hours andtwenty four hours as compared to the CALLAWAY GOLF RULE 35 SOFTFEEL golfballs. For example, the #4 golf ball of the present invention had a “b”measurement of 1.76 before exposure and a measurement of 8.37 after fourhours of exposure to sunlight. The #1 CALLAWAY GOLF RULE 35 SOFTFEELgolf ball had a b measurement of 4.6 before exposure and a measurementof 36.35 after four hours of exposure to sunlight. The golf balls wereexposed to sunlight on the rooftop of a building in Carlsbad, Calif.(latitude 32 46 30 north, longitude 117 25 06 west) on a winter day.Thus, not only do the covers 16 of the golf balls of the presentinvention have less yellowing to begin with, after exposure to sunlightthe covers 16 yellow less than other covers composed of thermosettingpolyurethane.

TABLE SIX Prepolymer Prepolymer Prepolymer Ball Blend NCO % CurativeBlend Temp. Blend press Ex. 8 LF930:DMMP 5.06 E100 120 175 Ex. 9LF930:DMMP 5.15 E100 117 185 Ex. 10 LF930/LF950:DMMP 5.67 E100 117 179Ex. 11 LF950:DMMP 6.18 E100/LNZA 107 207 Ex. 12 LFG960:DMMP 5.70E100/LNZA 113 212 Comp. 1 LFG960 — E100/LNZA 115 245 Comp. 2 LF930 —E100 120 209

TABLE SEVEN Plaque Plaque Curative Gel Gel Ball Hardness Flex. Mod.Temp. Temp. Time Ex. 8 50 9617 93 150 77 Ex. 9 49 10308 93 145 86 Ex. 1053 11987 93 150 81 Ex. 11 52 8343 91 150 94 Ex. 12 50 17843 90 150 90Comp. 1 — — 91 150 75 Comp. 2 — — 89 150 72

Tables Six and Seven illustrate the processing benefits of usingdimethyl methylphosphonate in a prepolymer blend. The dimethylmethylphosphonate, listed in the tables as “DMMP”, lowers the viscosityof the prepolymer blend thereby reducing the prepolymer blend pressureand the temperature for processing. The gel time is also slightlyincreased for the prepolymer blends containing dimethylmethylphosphonate. In Tables Six and Seven, all of the temperatures arein Fahrenheit, all of the pressure are in pounds per square inch, thehardness measurements are in Shore D and the flexural modulusmeasurements are in pounds per square inch. All of the curativescontained diethyl 2,4-toluenediamine (E100), with examples #11 and 12having 30 parts 4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline(LONZACURE) with 70 parts diethyl 2,4-toluenediamine (E100). As comparedto the comparison balls 1 and 2, the prepolymer blend pressure was muchlower as was the prepolymer blend temperature. The gel time was alsoslightly increased as compared to the non-dimethyl methylphosphonateprepolymer blends.

From the foregoing it is believed that those skilled in the pertinentart will recognize the meritorious advancement of this invention andwill readily understand that while the present invention has beendescribed in association with a preferred embodiment thereof, and otherembodiments illustrated in the accompanying drawings, numerous changes,modifications and substitutions of equivalents may be made thereinwithout departing from the spirit and scope of this invention which isintended to be unlimited by the foregoing except as may appear in thefollowing appended claims. Therefore, the embodiments of the inventionin which an exclusive property or privilege is claimed are defined inthe following appended claims.

1. A golf ball comprising: a core; and a cover formed over the core, the cover composed of a thermosetting polyurethane material formed from reactants comprising a prepolymer blend comprising a polyurethane prepolymer and dimethyl methylphosphonate, and a curing agent.
 2. The golf ball according to claim 1 further comprising at least one boundary layer disposed between the core and the cover.
 3. The golf ball according to claim 1 wherein the polyurethane prepolymer is a polypropylene glycol terminated toluene diisocyanate prepolymer with a nitrogen-carbon-oxygen content ranging from 3.0% to 6.0%.
 4. The golf ball according to claim 2 wherein the boundary layer is composed of a blend of ionomers.
 5. The golf ball according to claim 1 wherein the polyurethane prepolymer is a polytetramethylene ether glycol terminated toluene diisocyanate prepolymer with a nitrogen-carbon-oxygen content ranging from 3.75% to 7.0%.
 6. A golf ball comprising: a core comprising a polybutadiene mixture; a boundary layer formed over the core; and a cover formed over the boundary layer, the cover composed of a thermosetting polyurethane material formed from reactants comprising a prepolymer blend comprising polyurethane prepolymer and dimethyl methylphosphonate, and diethyl 2,4-toluenediamine.
 7. A golf ball comprising: a core; and a cover formed over the core, the cover composed of a thermosetting polyurethane material formed from reactants comprising prepolymer blend comprising a polypropylene glycol terminated toluene diisocyanate prepolymer and dimethyl methylphosphonate, and a curative blend comprising 4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline and diethyl 2,4-toluenediamine.
 8. A golf ball comprising: a solid core comprising a polybutadiene mixture; a boundary layer formed over the core, the boundary layer comprising a blend of ionomer materials; and a cover formed over the core, the cover composed of a thermosetting polyurethane material formed from reactants comprising prepolymer blend comprising a polypropylene glycol terminated toluene diisocyanate prepolymer and dimethyl methylphosphonate, and a curative blend composed of 4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline and diethyl 2,4-toluenediamine.
 9. The golf ball according to claim 8 wherein the blend of ionomer materials of the boundary layer is composed of a sodium neutralized ethylene/methacrylic acid, a zinc neutralized ethylene/methacrylic acid and a magnesium neutralized terpolymer of ethylene, methacrylic acid and n-butyl acrylate.
 10. A golf ball comprising: a core comprising a polybutadiene mixture, the core having a diameter ranging from 1.35 inches to 1.64 inches and having a PGA compression ranging from 50 to 90; a boundary layer formed over the core, the boundary layer composed of a blend of ionomer materials, the boundary layer having a thickness ranging from 0.020 inch to 0.075 inch, the blend of ionomer materials having a Shore D hardness ranging from 50 to 75 as measured according to ASTM-D2240; and a cover formed over the core, the cover composed of a thermosetting polyurethane material formed from reactants comprising a prepolymer blend comprising polypropylene glycol terminated toluene diisocyanate prepolymer and dimethyl methylphosphonate in a range of 1 to 10 parts per hundred parts of the comprising polypropylene glycol terminated toluene diisocyanate prepolymer, and a curative blend comprising 20 to 40 parts 4,4′-methylenebis-(3-chloro,2,6-diethyl)-aniline and 80 to 60 parts diethyl 2,4-toluenediamine, wherein the cover has a Shore D hardness ranging from 30 to 60 as measured according to ASTM-D2240, a thickness ranging from 0.015 inch to 0.040 inch. 